Process and means for transforming organic acids into ketones



April 8, 1930. J. w. BECKMAN PROGESS AND MEANS FOR TRANSFORMING ORGANIC ACIDS INTO KETONES Filed' Feb. 23, 1928 TURN Patented Apr. 8, 1930 UNITED STATES PATENT OFFIE JOHN W. BEGKMAN, 0F OAKLAND, CALIFORNIA Application filed February 23, 1928. Serial No. 256,468.

My invention has for its object the process of removing the acids usually found associated with hydrocarbons and their ultimate transformation into ketones and aldehydes, and apparatus for practicing the process.

- A further object is the process treatment of hydrocarbons, and especially a refining process for crude oils, whereby undesirable acid constituents are removed therefrom and a salt or salts of said acids is formed and which salt or salts is then broken up and ketones are liberated and returned to the said hydrocarbons.

. Other objects will appear from the drawing and specification which follow:

These objects I attain by vaporizing the hydrocarbon mixture having the acid contents and passing it in intimate contact through a mass of pulverulent alkali earth metal oxide with which the acid or acids react to form a saltor salts.

The salt or salts thus formed are then heated to a suificient degree to fi'ect their decomposition whereby'they are caused to liberate members ofthe ketone group which flow out with the treated vapors and are condensed therewith in any conventional manner thus giving a distillate free from acid and enriched by theketone content.

In a special adaptation of my process I em ploy apparatus having one portion thereof heated to a relatively lower temperature and a second portion thereof heated to a relatively higher temperature, the re-action of the acid with the alkali earth metal oxide taking place in the lower temperature portion whereby the salts are formed, and the ketones liberated in the other portion of the ap paratus.

The process is conducted in cy ole by passing the vapors first in one direction and then in the reverse direction through the chamber and simultaneously reversing the heat applications to the chamber portions, so that the vapors entering the apparatus are first exposed to the lower temperature and as they travel into the second portion of the apparatus they are exposed to the higher temperature.

The salts which have been formed at the -quired to the chambers 8 and 9 lower temperature and in the first stage of treatment, will, during the next cycle, be

heated to the higher temperature andbe de-' composed into ketones and flow out with the treated vapors.

By referring to the accompanying diagram my invention will be made clear.

The figure is a diagrammatic showing of a still adapted to vaporize crude oil and pass the same through a plurality of treatment chambers after which the vapors flowing from said chambers are condensed in any conventional way.

A still is indicated by the numeral 1 heated as by the oil burner 2, to vaporize the crude oil having an organic acid content and which may be supplied thereto through the delivery pipe 3.

The oil vaporoutlet pipes from the still are shown at 4, 5, respectively, and valves controlling said pipes at 6, 7.

A plurality of treatment chambers in se ries are shown at 8, 9 having discharge pipes 10, 11 the latter having control valves 12, 13 respectively.

The discharge pipes lead to a conventional condenser at 14 and heat is applied as reas by the burners 15, 16.

Assuming that the crude oil in the still 1, which it is desired to treat, has a naphthenic acid content, having a formula RCOOH (where R is generally representative of the hydrocarbon group having the formula C H n the said crude oil in the still 1, is then vaporized by the application of sufiicient heat from the burner 2, the valves 7 and 12 are closed, the oil vapors are then forced through the material in the chamber 8 which is heated by the burner 15 to a temperature of substantially 200 C. and from here they pass through a second treatment chamber 9 heated by the burner 16 to 400 C. after which they pass through the discharge pipe 11, valve 13, and are condensed convention ally at 14.

The treatmentchambers 8 and 9 are supplied with alkali earth-metal oxide and I have found pulverulent calcium oxide or equivalent hydrate or oxide to be well adapted to re-act with the naphthenic acid, thereupon forming a calcium salt of the .said acid which remains in the container 8 as a result of the reaction.

After the process has continued sufliciently to have formed a mass of this calcium salt the valves 6 and 13 are closed and the valves 7 and 12 opened,4the heat from the burner 15 for the chamber 8 is increased to 100 and the chamber 9 through the burner 16 allowed to cool down to 200.

7 The calcium oxide or metal compound containing oxygen in the container 9 will now react with the acid content of the fresh vapors passing first through the container 9, separating the acid from the vapors; while the previously formed acid salts in the chamber 8 will, under the higher temperature to which the chamber 8 has now'been raised, be decomposed into ketones'which will pass off with the treated vapors through the pipe 10 and be condensed at 14 as before.

The hydrocarbon vapors now freed from acid and enriched by the ketones and the calcium mixture in the chamber 8 will have been restored to its original condition of oxide, hydrate or equivalent;

The flow through the chambers 8 and 9 is again reversed and the process continued in cycle. I am well aware that where calcium oxide or calcium hydrate has been emplo ed as the material in the chamber 8, and w en the ketones have been released, there will be left calcium carbonate but this will be decomposed, releasing carbonic acid as which passes off when the vapors are con ensed and without contaminating them in any way and the remaining calcium oxide will be ready for further and repeated use.

When the ketone-is formed and released from the naphthenic acids in the above example, by the heat in the second stage, this ketone or ketones will have the general formula C H O.

After the ketone has been entirely released the direction of the vapor flow is again reversed and the chamber 8 allowed to cool down, chamber 9 is heated up as before and the process continues in cycle.

I claim:

1. The process of transforming organic acids containedin a hydrocarbon mixture into ketones and aldehydes which consists in forcing an intimate'contact of said mixture with a mass of pulverulent metal oxide while main t ained at a temperature of below 300 C. whereby the said acid is decomposed forming salts of said metal in said mass, then heating said mass to a temperature above 300 C. and decomposing said salts whereby ketones and aldehydes are given off.

2. The process of transforming organic acids contained in a hydrocarbon mixture into ketones and aldehydes, which consists in forcing an intimate contact of said mixture with a mass of pulverulent metal oxide while maintained at a temperature of below 300 C. whereby the said acid is decomposed formcycle.

JOHN W. BE CKMAN. 

